The present invention relates to a hair dye composition having markedly high dyeing power, can strongly impart the hair with an extremely vivid color ranging from yellow, red, blue to green, has less color fade over time and undergoes a small change in the color tone of the dye even after storage.
Hair dyes can be classified by the dye to be used therefor, or whether they have bleaching action of melanin or not. Typical examples include a two-part permanent hair dye composed of a first part containing an alkali agent, an oxidation dye and a direct dye such as nitro dye and a second part containing an oxidizing agent; and one-part semi-permanent hair dye containing an organic acid or an alkali agent, and a direct dye such as acid dye, basic dye or nitro dye.
The above-described permanent hair dye is however accompanied with the drawbacks that color tone imparted by an oxidation dye is not so vivid and the color of the hair dyed with a vivid-color producing nitro dye ordinarily employed as a direct dye markedly fades over time and becomes dull soon even if the color tone rightly after dyeing is very vivid (Japanese Patent Application Laid-Open (Kokai) No. Hei 6-271435).
Recently, hair dyes containing as a direct dye a so-called cationic dye having a cation group contained in their conjugate system have been reported (Japanese Language Laid-Open Publication (PCT) No. Hei 8-507545, 8-501322 or 10-502946, or Japanese Patent Application Laid-Open (Kokai) No. Hei 10-194942). They have been found to involve drawbacks that intended dyeing effects are not available owing to decomposition of them caused by mixing, upon hair dyeing, with hydrogen peroxide ordinarily employed as an oxidizing agent; and that when a cation group is contained in an azo-based (xe2x80x94Nxe2x95x90Nxe2x80x94) conjugated system, they are unstable to an alkali agent or a reducing agent essentially contained in a permanent hair dye.
An object of the present invention is to provide a hair dye composition which has high hair dyeing power, less color fade over time, and excellent storage stability to permit only a small change in color tone of the dye after storage.
The present inventors have found that when the below-described compounds known as photosensitizing dye or sensitizing dye [Journal of Synthetic Organic Chemistry, Japan, 32(12), 971-988 (1974), etc.] are used as a hair dye, the resulting dye composition can strongly impart the hair with a vivid color ranging from yellow, red, blue to green without decomposing the dye upon hair drying, exhibits excellent light resistance, washing resistance, perspiration resistance, friction resistance and heat resistance, and undergoes a small change in the color tone of the dye after storage as compared with that rightly after preparation because the dye exists in the composition stably.
In one aspect of the present invention, there is thus provided a hair dye composition comprising, as a direct dye, a compound represented by the following formula (I), (II), (III) or (IV): 
wherein, m stands for 0, 1 or 2, n stands for 1 or 2,
m units of R1 and n units of R4 each independently represents a hydrogen atom, a C1-4 alkyl group or a halogen atom, m units of R2 each independently represents a hydrogen atom, a C1-4 alkyl group or an aryl group, with the proviso that at m=2, two R2s, taken together with the adjacent xe2x95x90Cxe2x80x94CHxe2x95x90Cxe2x80x94, may form a carbocyclic structure or an oxygen-containing heterocyclic structure, n units of R3 each independently represents a hydrogen atom or a C1-4 alkyl group, n units of R5 each independently represents a hydrogen atom or a C1-4 alkyl group, or is bonded, via a group xe2x80x94COxe2x80x94Oxe2x80x94, to a ring B5 to form a lactone ring, R6 represents a hydrogen atom or a C1-4 alkyl group,
A1 represents the below-described formula (1), (2) or (3), A2 represents the below-described formula (4), A3 represents the below-described formula (5), (6), (7), (8) or (9), A4 and Z1 each independently represents the below-described formula (10), (11), (12), (13), (14), (15) or (16), Z2 represents the below-described formula (17), Z3 represents the below-described formula (18), (19), (20) or (21): 
xe2x80x83(in which, a broken line means presence or absence of xcfx80 bonding, D1 represents an oxygen atom, a sulfur atom or a group NR25, D2 represents an oxygen atom, a sulfur atom, a group NR26 or a group CR27R28, D3 represents a nitrogen atom or a group CR29, D4 represents an oxygen atom, a sulfur atom or a group NR30, R7, R8, R9, R14 and R25 each independently represents a C1-6 alkyl group which may have a substituent, R10, R11, R13, R15, R16, R21, R22, R27, R28 and R29 each independently represents a hydrogen atom or a C1-6 alkyl group, R12 and R26 each independently represents a hydrogen atom or a C1-6 alkyl group which may have a substituent, R17 and R18 each independently represents a hydrogen atom, a C1-6 alkyl group which may have a substituent or an aryl group which may have a substituent, or R17 and R18, taken together with the adjacent nitrogen atom, form a nitrogen-containing heterocycle or one or both of R17 and R18 is (are) bonded to the ring B5 to form a nitrogen-containing heterocycle, R19 and R23 each independently represents an aryl group which may have a substituent, R20 represents a C1-6 alkyl group, R24 and R30 each independently represents a hydrogen atom, a C1-6 alkyl group which may have a substituent, or an aryl group which may have a substituent, Y1 and Y2 each independently represents an oxygen atom or a sulfur atom, rings B1, B2, B3 and B4 each independently has a ring structure which may have, as a substituent, a halogen atom, an aryl group or a C1-4 alkyl group or may further be cyclocondensed with a benzene ring, B5 has a ring structure which may have, as a substituent, a halogen atom, an aryl group or a C1-4 alkyl group, may be condensed with a benzene ring, or may be bonded to R17 or R18 to have a ring structure which may be cyclocondensed with a nitrogen-containing heterocycle), and
Xxe2x88x92 represents an anion, with the proviso that Xxe2x88x92 does not exist when R7, R8, R9 and R25 each has a sulfonium group as a substituent.
In another aspect of the present invention, there is also provided a method for dyeing the hair with the above-described hair dye composition.
In the formulas (I) to (IV), m is preferably 0 or 1 and n is preferably 1 from the viewpoint of stability in the hair dye composition.
Examples of the C1-4 alkyl group represented by R1 or R4 include methyl, ethyl and butyl groups, those of the halogen atom include chlorine, bromine and fluorine atoms. As each of R1 and R4, a hydrogen atom is most preferred.
Examples of the C1-4 alkyl group represented by R2 include methyl, ethyl and butyl groups, those of the aryl group include phenyl group. Examples of the carbocyclic structure which may be formed at m=2 by two R2s when they are taken together with the adjacent xe2x95x90Cxe2x80x94CHxe2x95x90Cxe2x80x94 include cyclohexene ring and cyclopentene ring. As the oxygen-containing heterocyclic structure, 4H-pyrane ring can be mentioned as an example. These rings may be substituted by an alkyl group. As R2, hydrogen atom and C1-4 alkyl groups are preferred, of which the hydrogen atom, methyl group and ethyl group are particularly preferred.
Examples of the C1-4 alkyl group represented by R3 or R6 include methyl, ethyl and butyl groups. As each of R3 and R6, hydrogen atom is most preferred.
Examples of the C1-4 alkyl group represented by R5 include methyl, ethyl and butyl groups, while those of the lactone ring which may be formed by bonding of R5 to the ring B5 via xe2x80x94COxe2x80x94Oxe2x80x94 include coumalin ring (including ring B5). As R5, hydrogen atom is most preferred.
As examples of the substituents for the groups (1) to (21) represented by each of A1 to A4 and Z1 to Z3, the below-described ones can be mentioned.
Examples of the C1-6 alkyl group represented by R7, R8, R9, R12, R14, R25 or R26 include methyl, ethyl, propyl, isopropyl and cyclohexyl groups, which may each be substituted by an aryl (such as phenyl), sulfonium, carboxy or vinyl group. Particularly preferred examples of R7, R8, R9, R14 or R25 include methyl and ethyl groups, while those of R12 and R26 include hydrogen atom, methyl group and ethyl group.
Examples of the C1-6 alkyl group represented by R10, R11, R13, R15, R16, R20, R21, R22, R27, R28 or R29 include methyl, ethyl, butyl and hexyl groups. Particularly preferred examples of R10, R11, R13, R15, R16 and R29 include hydrogen atom, those of R20, R27 or R28 include methyl group, and those of R21 or R22 include hydrogen atom and methyl group.
Examples of the C1-6 alkyl group represented by R17 or R18 include methyl, ethyl, propyl, butyl, hexyl, isopropyl and cyclohexyl groups, which may each be substituted by an aryl group (such as phenyl), cyano group or halogen atom (such as chlorine atom). Examples of the aryl group represented by R17 or R18 include phenyl and naphthyl groups, which may each be substituted by an amino group. Examples of the ring which may be formed by R17 and R18 when they are taken together with the adjacent nitrogen atom include pyrrolidine, piperidine, morpholine and piperazine rings. Examples of the nitrogen-containing heterocycle which may be formed by bonding of either one or both of R17 and R18 to the ring B5 include julolidine ring (including ring B5). Particularly preferred examples of R17 or R18 include hydrogen atom, methyl group and ethyl group.
Examples of the aryl group represented by R19 or R23 include phenyl and naphthyl groups, which may each be substituted by a sulfonium group. As each of R19 and R23, unsubstituted phenyl group is most preferred.
Examples of the C1-6 alkyl group represented by R24 or R30 include methyl, ethyl, propyl, butyl, hexyl, isopropyl and cyclohexyl groups, which may each be substituted by an aryl (such as phenyl), carboxy or vinyl group. Examples of the aryl group represented by R24 or R30 include phenyl and naphthyl groups, which may each be substituted by a sulfonium group. Particularly preferred as each of R24 and R30 are hydrogen atom, methyl group and ethyl group.
As each of Y1 and Y2, an oxygen atom is more preferred.
As a substituent for each of the rings B1 to B5, examples of the halogen atom include chlorine, bromine and fluorine atoms, those of the aryl group include phenyl group, and those of the C1-4 alkyl group include methyl, ethyl and butyl. As each of the rings B1 to B5, an unsubstituted one is preferred. These rings may each be cyclocondensed with a benzene ring. The ring cyclocondensed with a benzene ring is preferred as well as the above-described uncyclocondensed ring.
Examples of the anion represented by Xxe2x88x92 in the formula (I) or (II) include chloride ions, bromide ions, iodide ions, trichlorozincic acid ions, tetrachlorozincic acid ions, sulfuric acid ions, hydrosulfuric acid ions, methyl sulfate ions, phosphoric acid ions, formic acid ions and acetic acid ions. When a group (R7, R8, R9 or R25) to be bonded to a nitrogen atom has a sulfonium group as a substituent, Xxe2x88x92 does not exist because a counterion is formed in the molecule.
In Compounds (I) to (IV), as A1, preferred are the groups (1) (particularly, D1=O, NR25) and (2); as A3, preferred are the groups (5) (particularly, D2=O, NR26, CR27R28), (6) and (8); as A4, preferred are the groups (10) (particularly, D2=O, NR26, CR27R28), (11), (12), (14) and (15); as Z1, particularly preferred are the group (10) (D2=O) when A1 is the group (1) (D1=O), the group (10) (D2=NR26) when A1 is a group (1) (D1=NR25), the group (11) when A1 is the group (2) (at 2-position), the group (12) when A1 is a group (2) (at 4-position); and as Z3, preferred are the groups (18), (19) and (21) (particularly, D4=NR30). Out of Compounds (I) to (IV), Compounds (I) to (III), particularly Compound (I) is preferred.
Specific examples of the direct dyes (I) to (IV) to be used in the present invention will next be shown. 
As a direct dye, at least one of these direct dyes (I) to (IV) can be used. It is also possible to use another direct dye in combination therewith. In particular, when the direct dye (I), (II), (III) or (IV) is a yellow dye, combination with red and blue dyes, when it is a red dye, combination with yellow and blue dyes, and when it is a blue dye, combination with yellow and red dyes, each makes it possible to dye the hair with a deep and highly lustrous dark brown or black color.
Examples of the direct dye other than the direct dyes (I) to (IV) include Basic Blue 7 (C.I. 42595), Basic Blue 26 (C.I. 44045), Basic Blue 99 (C.I. 56059), Basic Violet 10 (C.I. 45170), Basic Violet 14 (C.I. 42515), Basic Brown 16 (C.I. 12250), Basic Brown 17 (C.I. 12251), Basic Red 2 (C.I. 50240), Basic Red 22 (C.I. 11055), Basic Red 76 (C.I. 12245), Basic Red 118 (C.I. 12251:1) and Basic Yellow 57 (C.I. 12719); and basic dyes as described in Japanese Patent Publication No. Sho 58-2204, Japanese Patent Application Laid-Open (Kokai) No. Hei 9-118832, Japanese Language Laid-Open Publication (PCT) No. Hei 8-501322 or Japanese Language Laid-Open Publication (PCT) No. Hei 8-507545.
The direct dyes (I) to (IV) are each preferably added in an amount of 0.01 to 20 wt. %, more preferably 0.05 to 10 wt. %, especially 0.1 to 5 wt. % based on the whole composition (after mixture of all the component parts when the hair dye composition is a two part or three part type; this will apply equally hereinafter). When another direct dye is added in combination, the content of it in total with the direct dye (I), (II), (III) or (IV) preferably ranges from 0.05 to 10 wt. %, especially 0.1 to 5 wt. %.
The hair dye composition of the present invention is preferably adjusted to pH 6 to 11, with pH 8 to 11 being especially preferred. Examples of the alkali agent to be used for pH adjustment include ordinarily employed ones such as ammonia, organic amines and salts thereof. The alkali agent is preferably added in an amount of 0.01 to 20 wt. %, more preferably 0.1 to 10 wt. %, especially 0.5 to 5 wt. % based on the whole composition.
In the hair dye composition of the present invention, an oxidizing agent can be incorporated. In this case, hair dyeing and bleaching can be carried out simultaneously, which facilitates more vivid hair dyeing. Ordinarily employed oxidizing agents, for example, hydrogen peroxide, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, perborates such as sodium perborate, percarbonates such as sodium percarbonate and bromates such as sodium bromate and potassium bromate are usable. Out of them, hydrogen peroxide is especially preferred. The oxidizing agent is added in an amount of 0.5 to 10 wt. %, especially 1 to 8 wt. %, based on the whole composition.
In the hair dye composition of the present invention, an oxidation dye can be incorporated further. This incorporation enables markedly vivid dyeing not attainable by the single use of an oxidation dye. In this case, the above-exemplified oxidizing agents can be used as an oxidizing agent, with hydrogen peroxide being particularly preferred. Alternatively, an oxidizing enzyme such as laccase can be employed. For the oxidation dye, known color developers and couplers ordinarily employed for an oxidation type hair dye can be used.
Examples of the developer include p-phenylenediamines having one or several groups selected from groups NH2xe2x80x94, NHRxe2x80x94 and NR2xe2x80x94 (in which R represents a C1-4 alkyl or hydroxyalkyl group) such as p-phenylenediamine, p-toluylenediamine, N-methyl-p-phenylenediamine, chloro-p-phenylenediamine, 2-(2xe2x80x2-hydroxyethylamino)-5-aminotoluene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, 2,5-diaminoanisole, N-(2-hydroxypropyl)-p-phenylenediamine and N-2-methoxyethyl-p-phenylenediamine; 2,5-diaminopyridine derivatives and 4,5-diaminopyrazole derivatives; p-aminophenols such as p-aminophenol, 2-methyl-4-aminophenol, N-methyl-p-aminophenol, 3-methyl-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol and 2,5-dimethyl-4-aminophenol; o-aminophenols, o-phenylenediamines, 4,4xe2x80x2-diaminophenylamine and hydroxypropylbis(N-hydroxyethyl-p-phenylenediamine); and salts thereof.
Examples of the coupler include 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 5-(2xe2x80x2-hydroxyethylamino)-2-methylphenol, 2,4-diaminoanisole, m-toluylenediamine, resorcin, m-phenylenediamine, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 4-hydroxyindole, 6-hydroxyindole, 2,4-diamino-6=hydroxypyrimidine, 2,4,6-triaminopyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine and 1,3-bis(2,4-diaminophenoxy)propane; and salts thereof.
As each of a developer and a coupler, at least one of the above-exemplified ones can be used. Although no particular limitation is imposed on the content of each of them, it is added in an amount of 0.01 to 20 wt. %, especially 0.5 to 10 wt. % based on the whole composition.
To the hair dye composition of the present invention, a known autoxidation dye typified by an indole or an indoline, or a known direct dye such as a nitro dye or a disperse dye can also be added.
When an anionic component (such as anionic surfactant or anionic polymer) is added to the hair dye composition of the present invention in the case where the direct dye (I) or (II) to be incorporated in the composition is a cationic dye, it is preferred to satisfy the following equation:
xe2x80x9cIon activity concentration of the anionic component/ion activity concentration of the cationic direct dye (I) or (II) incorporated in the hair dye compositionxe2x89xa68xe2x80x9d
The term xe2x80x9cion activity concentrationxe2x80x9d as used herein means xe2x80x9cmolar concentrationxc3x97ionic valencexe2x80x9d.
Addition of a polyol, polyol alkyl ether, cationic or amphoteric polymer or silicone to the hair dye composition of the present invention is preferred, because the resulting composition can dye the hair uniformly and improve the cosmetic effects of the hair.
In addition to the above-described components, those ordinarily employed as a raw material for cosmetics can be added to the hair dye composition of the present invention. Examples of such an optional component include hydrocarbons, animal or vegetable fats and oils, higher fatty acids, organic solvents, penetration promoters, cationic surfactants, natural or synthetic polymers, higher alcohols, ethers, amphoteric surfactants, nonionic surfactants, protein derivatives, amino acids, antiseptics, chelating agents, stabilizing agents, antioxidants, plant extracts, crude drug extracts, vitamins, colorants, perfumes and ultraviolet absorbers.
The hair dye composition of the present invention can be prepared in a conventional manner into a one-part composition, a two-part composition having a first component part containing an alkali agent and a second component part containing an oxidizing agent, or a three-part composition having, in addition to these two component parts, a powdery oxidizing agent such as persulfate. The direct dye (I), (II), (III) or (IV) can be incorporated in either one or both of these component parts of the two-part or three-part composition. When the hair dye composition of the present invention is one-part type, it is applied to the hair directly, while when it is a two- or three-part type, it is applied to the hair after mixing these parts upon hair dyeing.
No particular limitation is imposed on the form of the hair dye composition of the present invention. Examples include powder, transparent liquid, emulsion, cream, gel, paste, aerosol, and aerosol foam. It preferably has a viscosity of 2000 to 100000 mpaxc2x7s in the stage of application to the hair (after mixing of all the components when the hair dye composition is a two-part or three-part type).